Reproduction of photographic images on ceramic surfaces



Nov. 10, 1964 M. N. GLADSTONE 3,156,562

REPRODUCTION OF PHQTOGRAPHIC IMAGES 0N CERAMIC SURFACES Filed 00's. 14. 1960 140.1. fig

INVENIQR. Adz/exam M fiznosrous United States Patent 3,156,562 REPRODUCTION GE PHOTGGRAPHHC IMAGES 0N CERAMIC SURFACES Murray N. Gladstone, Los Angeles, Calif. (532 E. Michelle St, West Covina, Calif.) Filed Oct. 14, 1960, Ser. No. 62,672 6 Claims. {CI. 96-34) The present invention relates to photographic reproduction, and more particularly to the reproduction of photographic images on ceramic surfaces.

Methods have been known in the prior art for the reproduction of photographic images on ceramic surfaces. Such known methods have usually presented a number of disadvantages. For example, line reproductions rather than continuous tone reproductions have ordinarily been obtained. This is to say that the reproductions obtained by the prior methods do not encompass the full tonal range of a photograph including all gradations from white through black, with all and every intermediate tone or shade of gray, as is present in an original photograph. As an additional disadvantage, the known methods have usually been quite complex, and have required specialized knowledge and training for their practice. Also, uniformity of results have usually not been obtainable when the known methods have been employed. In addition, the methods of the prior art have been limited in application as regards the employment of the usual photographic reproduction techniques and controls. Also, noticeable defects have been encountered in the finished product, such as blow-outs, holes, pealing, frilling, and tearing. Finally, the methods of the prior art have often not involved high fire ceramic techniques, and consequently have not produced the permanency of result which is obtainable only through the use of such techniques.

It is therefore an object of the present invention to provide a method of forming photographically faithful continuous tone or line reproductions on ceramic surfaces.

Another object of the invention is to provide a method of reproducing photographic images on ceramic surfaces, which method involves techniques and procedures understandable and workable by anyone who is versed in the art of photography and is acquainted with the usual dark room practices.

Another object of the present invention is to provide a method of reproducing photographic images on ceramic surfaces, the practice of which assures uniformity of the results obtained. 7

Another object of the invention is to provide a method of reproducing photographic images on ceramic surfaces, which method enables the use of many of the well-known photographic dark room controls.

Another object of the present invention is to provide a method of reproducing photographic images on ceramic surfaces, by which method images in most of the colors known to the ceramic art may be provided.

Another object of the invention is to provide a method of reproducing photographic images on ceramic surfaces, without causing any surface defects.

Another object of the invention is to provide a method for the reproduction of photographic images on ceramic surfaces, which method employs high fire ceramic techniques, and thus provides the permanency of results usually obtained by such techniques.

Another object of the invention is to provide an improved method for the creation of metallic printed electronic circuits.

Another object of the present invention is to provide an improved method for the preparation of lithographic offset printing plates.

3,156,562 Patented Nov. 10, 1964 Another object of the invention is to provide decorated ceramic articles which bear thereon continuous tone reproductions of photographic images.

Another object of the invention is to provide decorated ceramic articles which bear thereon full line reproductions of photographic images.

Another object of the invention is to provide a ceramic tile bearing thereon a printed electronic circuit.

Another object of the invention is to provide a lithographic oifset printing plate having a ceramic base.

These and other objects of the invention will become apparent from the following specification, read in conjunction with the accompanying drawings, in which:

FIGURE 1 is a plan view of a portion of photographic stripping film as seen from the back;

FIGURE 2 is a View similar to FIGURE 1, the film having been exposed to a selected negative, and having been developed, bleached to form a matrix, and partially stripped;

FIGURE 3 is a view similar to FIGURE 2, the matrix having been colored by a ceramic pigment, and the image having been accentuated by treatment with potassium permanganate;

FIGURE 4 is a top plan view of the colored matrix of FIGURE 3, adhered to an enameled tile;

FIGURE 5 is a View similar to FIGURE 4, the enameled tile having been treated with acetone;

FIGURE 6 is a View similar to FIGURE 5, the tile having been fired in a kiln;

FIGURE 7 is a vertical section taken along the lines 77 of FIGURE 2; and

FIGURE 8 is a vertical section taken along the lines 88 of FIGURE 4.

Referring to the drawings, and in particular to FIG- URE l, a portion of photographic stripping film 10 is shown. The film 10 is comprised of a thin photographic gelatin emulsion, laid upon a suitable base. A base of cellulose acetate or cellulose nitrate is preferred. A film that is particularly suited for the present process is Flexichrome Stripping Film (trademark), manufactured by the Eastman Kodak Company. This film is comprised of a photographic emulsion which is laid upon an exceedingly thin cellulose nitrate base, the latter in turn being laid upon a much heavier cellulose acetate base to give it firmness and stability in operation. The film 10 is exposed through the base to any desired photographic negative. The image thus produced is then developed by a suitable tanning developer, such as follows:

Grams Citric acid 3.2 Pyro gallol 128 Sodium sulphite 32 Ammonium chloride 24 Potassium bromide 24 Water to make 1 gallon.

Use 1 part to 10 parts water. Add 15 cc. of 10% sodium hydroxide to each 1000 cc. of working solution.

All developing procedures are emulsion side up, and the temperatures employed are preferably at 70 F., except where otherwise indicated. Developing time is, for example, 2 minutes.

Following development, the film is placed in the usual stop bath (e.g. 2% acetic acid for about 1 minute), and is then washed with warm water. The temperature of the wash is preferably F. The warm water will dissolve any gelatin which has not been hardened and tanned by the'developer to a depth'to which the exposure has been made. In the heavy shadow areas only a slight amount of gelatin will be dissolved away; in the highlight areas a larger amount of gelatin will be washed away; and in the middle tones an intermediate amount of gelatin will be Washed away. Since the film has been exposed through the base, the image remains held by the said base, while the remaining portions of the gelatin unafiected by the tanning agencies are washed away.

After the excess emulsion has thus been dissolved away, any emulsion adhering to the edges of the film is scraped away, such as, for example, by the fingernail. The film is then gently stripped, as by hand, under warm water (preferably 110 F.) and the nitrate base is thus pulled away from the acetate base. The nitrate base is then rinsed in warm water to dissolve away any of the adhesives which were employed to adhere the nitrate base to the acetate base. Three to five changes of warm water at 110 F. are preferred.

Cool water (85 90 F.) is then flowed over the film. This serves to cool the film and set the emulsion. The film is then bleached in accordance with standard procedure as noted below. The bleach serves to turn brown the black silver image which has been developed in the film. After rinsing, the brown image is removed by placing the film in a solution of sodium thiosulphate and acetic acid, and slightly agitating the film for a short time (eg. 60 seconds). A mixture of 75 cc. of 20% sodium thiosulphate solution in 125 cc. of 2% acetic acid solution, employed at 75 F. is particularly suitable for the purpose. The film is then washed in several changes of cool water (preferably about changes of water at 75 F.) for removal of the sodium thiosulphate-acetic acid solution, and the film is then hung on clips to dry. The film may be weighted at the bottom by means of clips attached to the bottom edge thereof to prevent curling, and may be swabbed with a thoroughly wetted and soft piece of hospital cotton for removal of any foreign specks therefrom. If increased contrast is desired, a repetition of the bleaching procedure may be carried out.

Another film which has been found particularly suited for the present invention is Kodalith Stripping Film (trademark), manufactured by the Eastman Kodak Company. Like Flexichrome, this film is provided with a thin cellulose nitrate base, laid upon a heavier cellulose acetate base. The procedure for preparing the matrix is much the same as described above, except for variations now to be noted.

When Kodalith Stripping Film is used, a positive of the photographic image desired may be employed. The film is developed in a low contrast developer, such as for example having the following formula:

Water at 125 F cc 750 Elon (trademark) (C H (GH) (NH-CH 1/2T-l SO l :4) grams-.. 7.5 Sodium sulphite-desiccated do 100 Water to make 1000 cc.

However, if exceedingly high contrast line work is desired, Kodalith Developer (trademark) may be employed or a high contrast developer such as for example having the following formula:

W'ater at 90 F cc 750 Sodium sulphitedesiccated grams 90 Hydroquinone (C H (OH) (1:4) do 45 Sodium hydroxide do 37.5 Potassium bromide do 30 Water to make 1000 cc.

The film after developing is bleached and etched, the following formula having been found particularly suitable for the purposes:

3% hydrogen peroxide cc 30 Cupric sulphate grams 20 Nitric acid cc 5 Potassium bromide cc .5

Water to make 1000 cc.

If a negative is employed as the starting point together with Kodalith Stripping Film, it is exposed through the 4. back, and a low contrast developer such as mentioned above is employed. The film is then bleached in the following solution:

Solution A Potassium permanganate gms 4 Water cc 1000 Solution B Sulfuric acid cc 20 Water cc 1000 The two solutions are mixed in equal proportions just before use. A bleaching temperature of about F. and a time of about seconds are preferred. After the bleach, the film is immersed in of 1% sodium bisulphite solution, washed, and exposed to white light, under water. It is then developed in a low contrast developer, washed, and etched in the hydrogen peroxide, etc. formula set forth above.

it should be noted that many other types of films may be employed, provided that they are not double coated. Also, the Flexichrome or Kodalith film mentioned above may be stripped after the addition of color precipitates (see below).

The stripped film portion 12 (FIGS. 2 and 7) now supports a matrix 14, rep esenting in clear gelatin all of the tonal values of the original negative.

The stripped film portion 12 supporting the imagebearing matrix 14 is treated with suitable chemicals for deposition within the matrix or" ceramic color precipitates. For this purpose, two baths are prepared, being maintained, for example, in two separate trays. One bath comprises a solution of one or more suitable soluble metallic salts, while the second bath comprises a solution of any chemical which will form a vitrifiable precipitate with the respective salts, which precipitate will provide the desired vitrifiable color. Since the chlorides of the metals which are soluble form the simplest compounds, these are preferably employed for the first bath. The second bath may be comprised of a hydroxide, carbonate, ferricyanide, or other soluble chemical which will form a metallic vitrifiable precipitate yielding a desired color, with a soluble metal in the first bath. Since carbonates and hydroxides are sometimes strong gelatin disintegrants, weak solutions of these must be used. The metallic salts may be employed in any solution up to saturation point, but a 20% solution has been found to often yield the best results.

Employing, for example, a 1% solution of sodium carbonate and a 20% solution of cobalt chloride (both at 70 F), the matrix is immersed alternately in the sodium carbonate and cobalt chloride solutions for a number of times in each, and is rinsed following each immersion. Tongs are preferably employed in handling the film. Thus, the matrix may be immersed in the sodium carbonate solution and gently rocked for a short period such as 10-15 seconds. The matrix is then rinsed for a few econds in clear water, and is then immersed in the cobalt chloride solution for a period of 10-15 seconds. The immersion and rinsing procedure is repeated preferably until the matrix has been immersed four times in the so dium carbonate solution and three times in the cobalt chloride solution. The matrix is then washed well, hung to dry, and swabbed for removal from the surface thereof of any foreign particles adhering thereto.

Many variations are possible in the above steps for forming the ceramic color precipitates within the matrix. For example, additional density may be attained by an additional number of immersions. Additional contrast may be obtained in the following manner: after sufiicient density in the shadow area has been attained, the film, in its dry state, is immersed in a of 1% solution of potassium permanganate for about thirty seconds, washed and dried. The film is then again treated with cobalt and carbonate in the manner above described, which treatment builds up greater densities in the shadow areas,

'5 leaving the highlight areas unaffected, and thereby increasing the contrast.

When iron or copper chloride is employed, the procedure is the same as that for cobalt chloride. However, other metals may require additional irnmersions and reimrnersions according to the density of the image desired.

After the matrix has been treated in the above manner with cobalt and carbonate, the image can only vaguely be seen and it is difficult to cut excess borders. It is therefore desirable to immerse the matrix in a solution of potassium permanganate. An immersion of about 25-30 seconds in a of 1% solution of potassium permanganate is preferred, and a fairly dark-brownish image 16 (FIG. 3) will result, permitting visual inspection. If iron or copper is employed instead of cobalt, the image will color sufficiently to be seen and handled without immersion in potassium permanganate solution.

A similar treatment to that described above is employed for the formation of silver, platinum or gold precipitates. In the case of gold and platinum, the chlorides may be employed together with sodium carbonate. However, in the case of silver, the nitrate is employed as one bath and sodium chloride as the other bath. The concentrations of the two solutions may here range from 20% to saturation.

To color with manganese, a different procedure is required. Here, the matrix is immersed in a solution of potassium permanganate (preferably of 5% concentration) for a period preferably of about 3-4 minutes. The potassium permanganate will form hydrated manganese dioxide in the gelatin, which will color the finished ceramic product in sepia.

The image oearing matrix 16 is then adhered to a ceramis base. Many types of ceramic glazed bases or glass bases may be employed to receive the image. An enamel coated copper tile has been found to provide a base which is expedient for a number of desirable end products, such as jewelry, lithographic plates (see below), and printed electronic circuits (see below).

A manner of preparing enamel tiles particularly suited for the present process will now be described. Sheet copper of any desired gage or thickness is cut to desired size, and the copper piece 18 (FIG. 8) is placed in a nitric acid bath of about 5% concentration for about 3 minutes. (The temperature of the bath and of all solutions employed in the preparation of the enamel tile being about 70 F.). The copper piece 1% is then washed and placed in a solution of sodium hydroxide of approximately 1% concentration for about 1 minute, and is then washed and placed in a conventional soapless detergent, employed as a solution of about /2 cupful per quart of water. The copper piece 13 is then dried by any convenient means, drying being possibly hastened by a gas flame.

Enamel is then applied to the copper piece 18 by sif ing through a wire mesh, by application in a damp state, or by spraying. The enamel used is copper enamel, which is available in three firing ranges: soft, medium and hard. Although any of the three may be employed, I prefer to use the medium range due to the fact that it fires at a medium heat, but does not scratch or chip as easily as the soft range enamel. Although any color of enamel may be employed, I prefer to use opaque white due to public familiarity with photographs on white backgrounds.

The first of two coats or layers of enamel applied is known as counter-enamelling. This coat 2% will serve to compensate for the differences between the coefi'icients of expansion of the copper and enamel, and is applied very thinly. The copper piece 18 bearing the first light enamel coat 20 then is placed in the kiln and removed when the kiln temperature reaches about 1400 F. After cooling, the copper piece 18 is then treated with nitric acid in the same manner as before, to loosen and remove fire glaze. The alkali and detergent baths just described are also again used, and the piece 18 is then dried.

The prime enamel coat or layer 22 may then be applied to the tile, this coat being 5-10 times thicker than that used for the counter-enamelling coat 20, and being designed to bear the final image. The tile is then placed in the kiln and fired at 1350 F. for '2-3 minutes, after which time it is removed. The tile 24 is then washed in running water to remove fire glaze. In order to avoid possible cracking when a transfer is placed on the enamel, the tile 24 is then refired in a kiln at 1150 R, which firing will cause the counter-enamel coat 29 on the bottom of the tile 24 to crack, and will relieve tensions in the prime enamel coat. After removal from the le'ln, the tile 24 is again washed under running water, and the edges thereof may be rubbed to remove any fire glaze.

The image-bearing matrix 16 may then be combined with the enamelled tile 24. To accomplish this, the matrix 16 is adhered to the prime enamel coat 22, emulsion face down, by means of a suitable adhesive. A preferred method for adhering the image-bearing matrix to the enamelled tile 24- will not be described. A solution of 50 grams of gum arabic in 506 cc. of boiling water is prepared, and is filtered through muslin and cooled. After cooling, 60 cc. of methanol are added as a preservative. The enamelled tile 24 held by tongs or tweezers is dipped into the solution. In its wet state, the tile 24 is laid upon a paper towel, face up. The matrix 16 is then set upon the tile, emulsion side down.

Excess gum arabic solution is then removed by means of a squeegee, the pressure employed being sufiiciently firm for the removal, but not so great as to cause damage to the matrix image. A layer as of gum arabic then remains between the matrix 16 and the enamel coat 22. The image bearing tile 28 (FIGS. 4 and 8) is then set aside to dry at room temperature for approximately three hours. However, drying may be hastened after about 15 minutes of drying at room temperature by means of a gas flame.

The cellulose nitrate base 12 is then removed by placing the image-bearing enamelled tile 28 in a tray containing acetone. The tile 28 should remain in the acetone for approximately three minutes, with slight agitation. Some crackling of the cellulose nitrate will be observed, and the disappearance of such crackling will serve as a visual indication that the cellulose nitrate has been completely dissolved. The tile should then be immersed in fresh acetone for approximately one minute, and should then be removed from the acetone and dried by any suitable means, such as blowing. Drying should be continued for at least 15 minutes. The image-bearing matrix 16 will then be more clearly seen (FIG. 5).

After the tile 28 has been thoroughly dried, it is placed in a kiln at between 900 degrees and 1000 degrees F., and it remains in the kiln until the temperature is between 1200 degrees and 1225 degrees F., at which time it is removed. At this temperature, the gum arabic and the gelatin vehicle have been burned away, leaving only the ceramic colorant on the surface of the enamel coat 22, and it will then be seen that the original photograph has been faithfully reproduced upon the ceramic tile 28, as shown at 3th (FIG. 6). The surface of the tile 28, at this time, has the same glossy appearance as before the application of the image-bearing matrix 16. It is believed that the original metallic precipitate is converted into an absorbed metallic silicate, becoming an integral part of the enamel surface. Images thus produced have been found to have permanent qualities and to be as fade proof as any colored ceramic.

The process of the invention can be employed for the creation of metallic printed electronic circuits. The process steps here are identical with those outlined above, with the exception of diiferences now to be noted, dealing with the coloring of the matrix. The starting point is a line negative of the original circuit. This is printed to size on the Flexichrome or other stripping film, the exposure being heavier than that used in printing an ordinary photographic image, since a heavier relief is required.

After formation of the matrix in the usual manner, it is colored by immersion alternately in solutions of silver nitrate and silver chloride. This forms a silver chloride precipitate within the heavy line relief of the circuit matrix. It has been found that best results are obtained when the matrix is immersed in each solution at least 15 times, so as to form a very heavy precipitate.

After washing and drying, the matrix is developed in a standard MQ. developer, such as, for example, the

following:

Vi ater at 125 F. cc 500 Elon "grams" 3 Sodium sulphite do Hydroquinone do 12 Sodium carbonate do 80 Potassium bromide do 2 Water to make 1000 cc.

A developer concentration of 1:1 is preferred, the development being carried on for about 2 minutes at 79 F. The image is then fixed, preferably for two minutes at F., in a 20% sodium thiosulphate solution and washed.

The matrix is then adhered to an enamelled tile in the manner above-described, and the cellulose nitrate film base removed. The matrix-bearing tile is then fired, preferably at 950 F., with removal from the kiln at 1050 F. Upon removal, some slag will usually be present on the surface of the enamel above the printed line, and can be removed by any suitable means, such as steel wool. he metallic silver lines on the surface of the enamelled tile will conduct electricity, although weakly. They are therefore strengthened by electroplating in known manner, and a useable printed circuit results. Printed circuits using metals other than silver which will conduct electricity, such as for example gold or platinum, may be similarly prepared by the use of solutions which form the appropriate metallic precipitates.

The process of the invention can also be employed for the preparation of a lithographic offset printing plate. {ere again, the procedures above-outlined are followed, except for some variations now to be noted.

In the formation of the matrix, any of the metal precipitates already discussed may be employed, including compounds of cobalt, iron, silver, and gold. For halftone work, the stripping film is exposed by contact with a half-tone screen of the original negative, and half-tone dots thus form the image in the matrix.

Prior to combination with the matrix, the surface of the enamelled tile is grained by any suitable means, such as, for example, sand blasting, grinding, or chemical treatment (e.g. with hydrofluoric acid). The matrix is combined with the enamelled tile in the manner above described, and the combined piece is fired at 950 F., with removal preferably at about 1l251150 F. The kiln temperatures thus employed will result in a slight softening of the surface of the enamelled tile without destruction of the grain formation. The bottom portion of the fired metallic image will be absorbed and held by the softened surface, while the remainder of the image will appear as raised in relief above said surface.

The plate thus formed is prepared for printing by flowing with an ink-receptive solvent such as turpentine, and then with a water-receptive adhesive such as gum arabic, followed by drying thereof. A thin film of water is then deposited within the grain by any suitable means, such as, for example, a damp felt roller. Lithographic ink is then applied to the plate, and will adhere only to the raised portions, the grained portions of the plate being nonreceptive to the ink due to the presence of the water film. The plate is then ready for offset or other printing.

If t e plate is treated with chemical reagents which affect either the enamel surface or the raised metallic image, without affecting the other, an etching process results, and a heightening of the image is thus provided.

8 For example, if gold carbonate has been used as the coloring precipitate, the final image will be in pure gold. The enamel surface can then be etched away by hydrofluoric acid. Conversely, if a copper image has been provided, treatment with nitric acid will result in an etching away of the image, and a depression will be formed in the enamel surface corresponding to the image. The surface can be then treated to hold in the depression, and used for a printing plate.

A depression in the plate can also be formed by abrading the image with fine steel wool or other abrasive less hard than the ceramic surface.

It follows that the original negative may be a half tone screen negative. The present process is capable of reproducing evcn the finest of dots in complete detail, and a lithographic plate in ceramics is thus obtainable which may have a much longer life than the softer printing plates presently in use.

It has been found that a matrix bearing a silver image, prepared as above, may be fired not only upon enamel or other ceramic surfaces, but also upon other materials which are a le to withstand kiln firing temperatures. Among such materials suitable for the purpose are copper, brass, steel, stainless steel and mica.

Although the present invention has been described with reference to particular embodiments thereof, it will be understood that various changes and modifications may be made therein without departing from the spirit of the invention or the scope of the appended claims.

I claim:

1. A process of producing a grainless photographic image in continuous tone on a ceramic surface from a stripping film having a gelatin silver halide emulsion adhered to a thin cellulose derivative support which is adhered by a warm-water softenable adhesive to a heavier cellulose derivative support, comprising the steps of exposing, through a continuous tone negative, the said emulsion so that the exposing light goes first through the cellulose derivative supports and then into the emulsion, developing the exposed film in a hardening developer which hardens the emulsion to a depth in direct proportion with the continuous tones of the said continuous tone negative, thus rendering insoluble in warm water all the portions of the emulsion so exposed and developed, arresting the developing action in a solution of acetic acid, washing away the unexposed portions of the emulsion with warm water, bleaching the resulting image in solutions of that class of chemicals which form an insoluble silver salt image soluble in thiosulphate solutions, dissolving said silver salt image in a thiosulphate solution, washing away the said thiosulphate solution, stripping under warm water the thin cellulose derivative support from the heavier cellulose derivative support, drying, treating the resulting clear gelatin relief image which is adhered to the thin cellulose derivative support alternately in aqueous solutions of metallic acid salts the metallic components of which are of the class consisting of ceramic colorants, and in aqueous solutions of alkali salts Within that class which will form insoluble metallic precipitates with the said metallic acid salts, resulting in the deposition within the gelatin relief image of a uniformly dispersed precipitate of water insoluble metallic salts the metallic components of which are of the class consisting of ceramic colorants and which metallic components will serve as the ceramic colorants herein, continuing the said alternate treatments until the required density of precipitate within the said gelatin relief image is obtained, swabbing the relief image to remove adhering surface precipitate, drying, adhering with an adhesive colloid the face of the precipitate bearing gelatin relief image to the ceramic surface, dissolving away the cellulose derivative support of the gelatin relief image, and firing the combined precipitate bearing gelatin relief image and the ceramic piece to burn away the gelatin and the adhesive colloid and to fuse the image to the ceramic piece.

2. A process of producing a grainless photographic image in continuous tone on a ceramic surface from a single coated photographic film, having a gelatin silver halide emulsion adhered to a cellulose derivative base, comprising the steps of exposing through a continuous tone negative the said emulsion so that the exposing light goes first through the cellulose derivative base and then into the emulsion, developing the exposed film in a hardening developer which hardens the emulsion to a depth in direct proportion with the continuous tones of the said continuous tone negative, thus rendering insoluble in warm Water all the portions of the emulsion so exposed and developed, arresting the developing action in a solution of acetic acid, washing away the unexposed portions of the emulsion with warm water, bleaching the resulting image in solutions of that class of chemicals which form an insoluble silver salt image soluble in thiosulphate solutions, dissolving said silver salt image in a thiosulphate solution, washing away the said thiosulphate solution, drying, and treating the resulting clear gelatin relief image, adhered to the cellulose derivative base, in the same manner and procedure as in claim 1.

3. A process of producing a grainless photographic image in continuous tone on a ceramic surface from a single coated photographic film having a gelatin silver halide emulsion adhered to a cellulose derivative base, comprising the steps of exposing, through a continuous tone positive, the said emulsion, developing, fixing in a thiosulphate solution, washing, etching away the developed image in a hydrogen peroxide etching solution, washing, drying, and treating the resulting clear gelatin relief image, adhered to the cellulose derivative base, in the same manner and procedure as in claim 1.

4. A process of producing a grainless photographic image in continuous tone on a ceramic surface from a gelatin coated temporary support, comprising the steps of sensitizing the said gelatin coated temporary support in a dichromate sensitizer, adhering to the surface of the sensitized gelatin coating thereof, while in its wet state, a sheet of transparent cellulose derivative film, drying in darkness, exposing the dichromate sensitized gelatin under a continuous tone negative so that the exposing light goes first through the cellulose derivative film adhering to the sensitized gelatin and then into the sensitized gelatin to harden said gelatin to a depth in direct proportion with the continuous tones of the said continuous tone negative, removing under Water the temporary support, washing in warm water the remaining gelatin adhered to the cellulose derivative film to remove the unexposed and unhardened portions of the gelatin, drying, treating the resulting gelatin relief image which is adhered to the cellulose derivative film alternately in aqueous solutions of metallic acid salts the metallic components of which are of the class consisting of ceramic colorants, and in aqueous solutions of alkali salts Within that class which will form insoluble metallic precipitates with the said metallic acid salts, resulting in the deposition withinthe gelatin relief image of a uniformly dispersed precipitate of water insoluble metallic salts the metallic components of which are of the class consisting of ceramic colorants and which metallic components willserve as the ceramic colorants herein, continuing the said alternate treatments until the required density of precipitate within the said gelatin relief image is obtained, swabbing the relief image to remove adhering surface precipitate, drying, adhering with an adhesive colloid the face of the precipitate hearing gelatin relief image to the ceramic surface, dissolving away the cellulose derivative support of the gelatin relief image, and firing the combined precipitate bearing gelatin relief image and the ceramic piece to burn away the gelatin and the adhesive colloid and to fuse the image to the ceramic piece.

5. A process of producing a grainless photographic image in continuous tone on a ceramic surface from a single coated film consisting of a gelatin coating adhered to a cellulose derivative base, comprising the steps of sensitizing the said gelatin coating in a dichromate sensitizer, drying in darkness, exposing the dichromate sensitized gelatin under a continuous tone negative so that the exposing light goes first through the cellulose derivative base and then into the sensitized gelatin adhered thereto, to harden said gelatin to a depth in direct proportion with the continuous tones of the said continuous tone negative, Washing in warm water to remove the unexposed and unhardened portions of the gelatin, drying, and treating the resulting gelatin relief image adhered to the cellulose derivative base in the same manner and procedure as in claim 4.

6. A process of producing a grainless photographic image in continuous tone on a ceramic surface from a photographic paper consisting of a gelatin silver halide emulsion adhered to a paper base, which emulsion has been exposed under a continuous tone negative, developed to a silver image, fixed in a thiosulphate solution and Washed, which paper is hereinafter referred to as the photographic paper, and from a gelatin coated paper which has been treated in and impregnated with an aqueous solution of a dichrornate, potassium ferricyanide, potassium bromide, and chromic acid, which paper is hereinafter referred to as the sensitized paper, comprising the steps of adhering the gelatin surface of the sensitized paper immediately after its removal from the above aqueous solution to the image surface of the photographic paper, so that the silver image of the photographic paper reacts with the dichromate, potassium ferricyanide, potassium bromide and chromic acid within the gelatin of the sensitized paper to harden said gelatin to a depth in direct proportion with the amount of silver in the photographic paper at any and every point of contact, so that said gelatin is hardened to a depth in direct proportion with the continuous tones of the said continuous tone negative, peeling the sensitized paper from the photograpic paper after such reaction has taken place, adhering a sheet of cellulose derivative film to the gelatin surface of the sensitized paper, removing under warm water the paper base of the sensitized paper, washing in warm water the gelatin remaining adhered to the cellulose derivative film to remove unhardened gelatin, drying, and treating the remaining gelatin relief image adhering to the cellulose derivative film in the same manner and procedure as in claim 1.

References Cited by the Examiner UNITED STATES PATENTS 2,043,025 6/ 36 Wooles.

2,650,878 9/53 Boyer 96-38 2,748,000 5/56 Mader 96-60 2,810,648 10/57 Hineline 96-60 2,914,404 11/59 Fanselau et al.

2,947,626 8/60 Famely et a1. 96-34 2,980,533 4/61 Charlton 96-34 OTHER REFERENCES Photo Ceramics-Basic Processes and Formulas, Ceramic Industry, February 1946, pp. 54-55.

NORMAN G. TORCHIN, Primary Examiner.

ARTHUR P. KENT, Examiner. 

1. A PROCESS OF PRODUCING A GRAINLESS PHOTOGRAPHIC IMAGE IN CONTINUOUS TONE ON A CERAMIC SURFACE FROM A STRIPPING FILM HAVING A GELATIN SILVER HALIDE EMULSION ADHERED TO A THIN CELLULOSE DERIVATIVE SUPPORT WHICH IS ADHERED BY A WARM-WATER SOFTENABLE ADHESIVE TO A HEAVIER CELLULOSE DERIVATIVE SUPPORT, COMPRISING THE STEPS OF EXPOSING, THROUGH A CONTINUOUS TONE NEGATIVE, THE SAID EMULSION SO THAT THE EXPOSING LIGHT GOES FIRST THROUGH THE CELLULOSE DERIVATIVE SUPPORTS AND THEN INTO THE EMULSION, DEVELOPING THE EXPOSED FILM IN A HARDENING DEVELOPER WHICH HARDENS THE EMULSION TO A DEPTH IN DIRCET PROPORTION WITH THE CONTINUOUS TONES OF THE SAID CONTINUOUS TONE NEGATIVE, THUS RENDERING INSOLUBLE IN WARM WATER ALL THE PORTIONS OF THE EMULSION SO EXPOSED AND DEVELOPED ARRESTING THE DEVELOPING ACTION IN A SOLUTION OF ACETIC ACID, WASHING AWAY THE UNEXPOSED PORTIONS OF THE EMULSION WITH WARM WATER, BLEACHING THE RESULTING IMAGE IN SOLUTIONS OF THAT CLASS OF CHEMICALS WHICH FORM AN INSOLUBLE SILVER SALT IMAGE SILUBLE IN THIOSULPHATE SOLUTIONS, DISSOLVING SAID SILVER SALT IMAGE IN A THIOSULPHATE SOLUTION, WASHING AWAY THE SAID THIOSULPHATE SOLUTION, STRIPPING UNDER WARM WATER THE THIN CELLULOSE DERIVATIVE SUPPORT FROM THE HEAVIER CELLULOSE DERIVATIVE SUPPORT, DRYING, TREATING THE RESULTING CLEAR GELATIN RELIEF IMAGE WHICH IS ADHERED TO THE THIN CELLULOSE DERIVATIVE SUPPORT ALTERNATELY IN AQUEOUS SOLUTIONS OF METALLIC ACID SALTS OF THE METALLIC COMPONENTS OF WHICH ARE OF THE CLASS CONSISTING OF CERAMIC COLORANTS, AND IN AQUEOUS SOLUTIONS OF ALKALI SALTS WITHIN THAT CLASS WHICH WILL FORM INSOLUBLE METALLIC PRECIPITATES WITH THE SAID METALLIC ACID SALTS, RESULTING IN THE DEPOSITION WITHIN THE GELATIN RELIEF IMAGE OF A UNIFORMLY DISPERSED PRECIPITATE OF WATER INSOLUBLE METALLIC SALTS THE METALLIC COMPONENTS OF WHICH ARE OF THE CLASS CONSISTING OF CERAMIC COLORANTS AND WHICH METALLIC COMPONENTS WILL SERVE AS THE CERAMIC COLORANTS HEREIN, CONTINUING THE SAID ALTERNATE TREATMENTS UNTIL THE REQUIRED DENSITY OF PRECIPITATE WITHIN THE SAID GELATIN RELIEF IMAGE IS OBTAINED, SWABBING THE RELIEF IMAGE TO REMOVE ADHERING SURFACE PRECIPITATE, DRYING, ADHERING WITH AN ADHESIVE COLLOID THE FACE OF THE PRECIPITATE BEARING GELATIN RELIEF IMAGE TO THE CERAMIC SURFACE, DISSOLVING AWAY THE CELLULOSE DERIVATIVE SUPPORT OF THE GELATIN RELIEF IMAGE, AND FIRING THE COMBINED PRECIPITATE BEARING GELATIN RELIEF IMAGE AND THE CERAMIC PIECE TO BURN AWAY THE GELATIN AND THE ADHESIVE COLLOID AND TO FUSE THE IMAGE TO THE CERAMIC PIECE. 